Yarn conditioning process



Patented Apr. 9, 1940 UNITED STATES PATENT OFFICE YARN CONDITIONING PROCESS New Jersey No Drawing. Application December 16, 1938,

Serial No. 246,204

13 Claims.

This invention relates to the conditioning of textile yarns and more particularly to the conditioning of filaments and yarns composed of organic derivatives of cellulose such as cellulose acetate, cellulose propionate, cellulose acetate propionate, and cellulose acetate butyrate, to render them more amenable to textile operations such as knitting and the like.

As is well known in the manufacture of yarns, particularly those composed of or containing cellulose organic derivatives, it is necessary to treat the yarn in order to reduce the tendency toward breakage of the individual filaments or fibers when they are subjected to various mechanical strains and to lubricate the yarn in order to facilitate handling in such operations as spinning, twisting, winding, and reeling. It is also necessary to treat yarn to adapt it for use as warp or filling or for the manufacture of various types of knitted fabrics. In knitting, it is particularly important that the yarn be soft and pliable in order that it may conform readily to the contour of the needles and thus produce a closely knit fabric free from such defects as stitch distortion, pin holes, laddering, and the like.

Heretofore it has been proposed to employ softening agents such as polyhydric alcohols and similar agents as ingredients of yarn conditioning or lubricating formulas, generally in connection with mineral, animal or vegetable oils. It has been found, however, that most of the known softening agents and the various formulas containing them have certain drawbacks, one of the most serious of which is high vapor pressure, and in some cases too drastic a solvent action on the yarn. Many of such agents possess slight or insuflicient solvent power for the lubricants with which they are used, and it is accordanigly necessary to employ blending agents or emulsifying agents in order to obtain operable yarn treating formulas. In addition, many of the known softening and lubricating agents are insufficiently soluble in water to permit satisfactory removal by aqueous scour baths.

This invention has as its principal object to provide an entirely new class of yarn conditioning agents which are particularly adapted for the treatment of yarns composed of or containing organic derivatives of cellulose and capableoflubrieating, softening and rendering such yarns more amenable to knitting and other textile operations. A further and specific object is to provide a class of conditioning agents which augment or assist the lubricating actionof various lubricants when applied to such yarns. A still further object is to provide yarn softening and lubricating formulas which can be readily removed from the yarns by the usual scour baths. A still further object is to provide an improved method for the conditioning of yams, particularly those composed of or 6 containing organic derivatives of cellulose such as cellulose acetate, whereby the yarn is rendered soft and pliable and capable of employment in a variety of textile operations where complicated designs or stitches are employed. Another object 10 is to provide an improved type of yarn which is especially amenable to textile operations, including circular knitting, weaving, spinning and the like. Other objects will appear hereinafter.

These objects are accomplished by the following invention which, in its broader aspects, comprises the discovery that esters of furfuryloxy and tetrahydrofurfuryloxy acetic acids having the general formulasz me on, 11-0 n c m0 CHr-C o-o R and HCCH

where R is an organic radical selected from the group consisting of the substituted and unsubstituted alkyl, cycloalkyl, aryl, heterocyclic and polyalkoxy groups, may be used as yarn conditioning agents and particularly as softening agents, with or without the addition of animal, mineral, or vegetable oils, in the treatment of yarns composed of or containing organic derivatives of cellulose. We have found that these compounds when employed as described in the detailed examples set forth below have a slight sol- 40 vent and/or softening action on cellulose organic derivative yarns which renders such yarns soft and pliable without at the same time having too drastic an action thereon.

These compounds may be prepared by treating furfuryloxy and tetrahydrofurfuryloxy acetic acids with the desired alcohol using a suitable catalyst .such as hydrochloric, sulfuric, p-toluene sulfonic, sulfo-sali'cylic acids, etc. Water formed in the reaction may be removed by means of azeotropic distillation or by treating a suitable alcohol with the acid chlorides of the above named acids. Mixed esters may be prepared by a combination of any of the known methods. So far as we are informed. the above-mentioned derivatives and V pressure.

fatty acid, or they may beprepared by treating the alcohol with a Grignard reagent, and reacting the product with a halogenated fatty acid. The following examples are illustrative.

Tetrahydrofurfuryloxyacetic acid 5 kg. of dry tetrahydrofurfuryl alcohol is placed in a 12-liter flask and reacted with 460 g. (20 g.- atoms) of sodium at C. or above. 945 g. of chloroacetic acid in 2 liters of tetrahydrofurfuryl alcohol are then added dropwise, with stirring, over a period of 2 hours. When the reaction is complete, most of the free tetrahydrofurfuryl alcohol is removed by distillation under reduced Hydrochloric acid is then added until the mixture is just acid to Congo red. The sodium chloride produced is filtered out, and the residue is fractionated under reduced pressure. An excellent yield of tetrahydrofurfuryloxyacetic acid, boiling at 153-155 C. at 4 mm. pressure, is produced.

5-M ethyl tetrahydro'furfuryloxyacetic acid 7 kg. of dry 5-methyl tetrahydrofurfuryl alcoholis placed in a 12-liter flask, and reacted with 1120 g. of potassium hydroxide. 945 g. of chloroacetic acid is added, and the reaction prodnot is worked up as described in the preceding example. 5-methyl tetrahydrofurfuryloxyacetic acid boils at 157-160" C. at 4 mm. pressure.

a-Furfuryloxy propio'nic acid Example 1 160 gm. of tetrahydrofurfuryloxy acetic acid are placed in a 1-liter flask with 600 cc. of butanol and 10 cc. of sulfuric acid and allowed to stand for several days. The mixture is then made neutral to litmus with sodium bicarbonate and distilled. The n-but3Ll esteijboils at 1l0-115 3 mm.

Example 2 160 gm. of tetrahydrofurfuryloxyacetic acid are placed in a 2-liter flask equipped with a column; condenser, separator and return tube from separator. Then 500 cc. of toluene, 200 gm. of methoxy ethanol, and 1 gm. of p-toluene sulfonic acid are added. The solution is then distilled to remove the water formed .due to esterification. When the reaction is complete (5-6 hr.) the solution is neutralized with sodium bicarbonate' and distilled. The p-methoxyethyl ester of tetrahydrofurfuryloxyacetic acid boils at 133- /3 mm.

Example 3 In a flask equipped as described above are placed 106 gm. of diethylene glycol, 1 gm. p-toluene sulfonic acid, 600 cc. xylene, and 320 gm. of

tetrahydrofurfuryl-oxyacetic acid. Esterification is carried out as described above. The ditetrahydrofurfuryloxy acetate of diethylene glycol boils at 240-5/3 mm. There .is also obtained some of the mono ester.

In accordance with the invention these compounds may be applied directly to the yarn during or after spinning, or may be added to the spinning solution itself. We have found that these compounds have exceptional solvent powers which enable them to dissolve mineral oils and blown and unblown, drying and semi-drying, vegetable and animal oils and accordingly they may be, and preferably are, employed as ingredients of yarn conditioning or lubricating formulas in conjunction with agents which function wholly or partially as lubricants.

In the following examples and description we have set forth several of the preferred embodiments of our invention, but they are included merely for purposes of illustration and not as a limitation thereof.

Our invention will be more readily understood I by reference to the following examples in which typical applications of the invention are set forth.

Example 4 the yarn.

Example 5 A conditioning liquid is made up as follows:

Parts Benzyl 5-methyl furfuryloxyacetate '70 Olive oil 30 and applied to textile materials such as silk, wool, cellulose acetate, viscose, etc. as described in Example 1. If the yarn is intended primarily for knitting, the amount of conditioning liquid applied may vary from 4-25% by weight of the yarn, and if the yarn is intended for weaving, the amount of liquid applied may vary between 1-5% by weight of the yarn. Cellulose acetate filaments or fibers treated as described are quite soft and pliable and give improved results in various textile operations such as weaving, knitting, etc. Other examples of suitable lubricants which are used as illustrated in Examples 4 and 5 follow:

Blown sperm oil 30 Diethylene glycol ditetrahydrofurfuryloxyacetate 20 Blown soya bean oil 80 Example 13 A 20% solution of cellulose acetate in acetone, in which is incorporated 1-25% by weight of the cellulose acetate of glycerol tritetrahydrofurfuryloxyacetin, is extruded through fine orifices into an evaporative atmosphere. The filaments thus produced are wound, or twisted and wound. Yarns thus produced are pliable and suitable for knitting.

Any of the above compositions may be applied to the yarn intended for use in circular knitting by means of a bath, wick, spray, roller, pad or any suitable means. The amount of conditioning liquid applied may vary between 25% by weight of the yarn. Usually, however, the amount of conditioning liquid applied is about -15% by weight of the yarn. Yarn composed of cellulose acetate conditioned as described above gives excellent results when used in the circular knitting process.

As will be apparent from the above examples and description the conditioning agents of our invention may be applied by a wide variety of methods. For example, we may employ the agent as an ingredient of the spinning dope from which the filaments are formed, the amount of the agent so employed depending upon a number of factors, such as the particular cellulose derivative used in making the yarn, the solvent or solvent combination used in making up the spinning solution, and the degree of softness or pliability desiredin the yarn, etc.

If the conditioning agent is to be applied to the yarn after spinning, this may be done by bringing the yarn in contact with a wick, roll, or felt wet therewith, or the liquid may be applied by immersion, spray, or otherwise. The particular point at which the liquid is applied may vary. It may, for example, be applied to the yarn inside or outside the spinning cabinet, between the guide and godet roll, between the godet or other roll or guide and the point of winding and/or twisting. In some cases, the

liquid may even be applied to the yarn after 'winding onto cones, spools, bobbins, or the like or by the so-called bobbin to bobbin" method. In the case of staple fiber manufacture, the liquid may be applied to the yarn prior to, or after cutting into staple lengths.

The amount of the agent so employed will vary widely depending upon the results desired, the specific nature of the material to which the agent is applied, the use to which the yarn is eventually to be put and other factors. For example, in a given case where acellulose organic acid' ester yarn such as a yarn composed of cellulose acetate, is intended for knitting, about 4m 25% or more by weight, based on the weight of the dry yarn, may be satisfactory, while if the yam is intended for weaving, the

amount may vary between about 1 and 5%.

Although in the above examples we have referred primarily to yarntreating compositionscontaining only the conditioning agent and an oil, other ingredients such as solvents,. nonsolvents, emulsifying agents, blending agents and thelike, may be added within the scope of our invention. Likewise, various dyes or other coloring matter may be included in case it is desired to permanently or fugitively tint or dye the material undergoing treatment.

Although we have found it convenient to illustrate our invention by reference to compositions containing specific percentages of the various ingredients, these percentages may vary widely depending upon the particular purposefor which the composition is intended. For example, if it is desired to control the solvent or softening action of the conditioning agent, the amount of the agent-may be adjusted as, for example, by reducing the amount of the agent and correspondinglyincreasing the amount of oil or other ingredient.

While we have described our invention with particular reference to the treatment of yarns composed of organic derivatives of cellulose such as cellulose acetate, the conditioning agents and formulas described herein are applicable to the conditioning of many other types of cellulose derivative yarns such as those composed of or containing cellulose propionate, cellulose butyrate, cellulose acetate propionate. cellulose acetate butyrate, ethyl cellulose, methyl cellulose, benzyl cellulose and others, as well as to the conditioning of silk, wool, cotton, viscose and other natural or artificial materials.

The term yarn as used herein and in the claims is to be understood as including a single filament, a plurality of filaments associated into the form of a thread, either of high or low twist, single or multiple threads associated or twisted together, composite threads composed of a'mixture of natural and artificial filaments or a composite thread formed by twisting together individual strands of natural or artificial materials, as well as cut staple fibers produced from natural and/or artificial filaments or threads and spun yarn produced from such staple fibers.

As indicated above, the yarn conditioning agents of our invention are exceptionally good solvents for a wide variety of mineral, blown and unblown, drying and semi-drying animal and vegetable oils such as cottonseed, olive, castor, neats-foot, sperm and other oils. This enables them to be used with any of such oils in making up a variety of yarn treating formulas of varying composition.

The yarn conditioning method and compositions of our invention possess many outstanding advantages. The fundamental and outstanding characteristic of the agents employed in accordance with the invention is their ability to soften yarns, especially those composed .of or containing organic derivatives of cellulose such as cellulose acetate and render them soft and pliable and amenable to various textile operations, especially operations such as those involved in weaving and knitting where complicated designs or stitches are employed, without too drastic an action on the yarn material. Another outstanding characteristic of these compounds is their exceptional solvent power for a wide variety of mineral, animal, and vegetable oils and their ability to act as lubricating assistants in conjunction wlth these oils when applied to such yarns. In addition, due to their solubility in water, they may be readily removed from yarns and fabrics by means of the usual aqueous scour baths. By employing the yarn conditioning agents and method of our invention as herein described, one is enabled to obtain highly satisfactory results in the manufacture of yarns and woven fabrics and especially the production from these yarns of closely knit fabrics free from defects such as pin holes, stitch distortion, laddering and the like.

What we claim and desire to secure by Letters Patent of the United States is:

l. The process of. conditioning yarn to render it moreamenable to textile operations including knitting, weaving, spinning and the like, which comprises applying thereto a lubricating and softening composition containing as its essential lubricating and softening component an ester of furfuryloxy and tetrahydrofurfuryloxy acetic acids having the general formulas:

where R is an organic radical selected from the group consisting of the substituted and unsubstituted alkyl, cycloalkyl, aryl, heterocyclic and polyalkoxy groups.

2. The process of conditioning yarn composed of or containing organic derivatives of. cellulose to render it more amenable to textile operations including knitting, weaving, spinning and the like, which comfiises applying thereto a lubricating and softening composition containing as its essential lubricating and softening component an ester of furfuryloxy and tetrahydrofurfuryloxy acetic acids having the general formulas:

H,O-0H1 H70 CH--CHr-OCHr-COOR H o and lHfififl HO CCHr-0CHz-C0OR where R is an organic radical selected from the group consisting of the substituted and unsubstituted alkyl, cycloalkyl, aryl, heterocyclic and polyalkoxy groups.

, 3. The process of conditioning yarn composed of or containing cellulose acetate to render it more amenable to textile operations including knitting, weaving, spinning, and the like, which comprises applying thereto a lubricating and softening composition containing as its essential lubricating and softening component an ester of furfuryloxy and tetrahydrofurfuryloxy acetic acids having the general formulas:

H-C CH-OHa-OCHr-C 0-011 and J HO C-CHz-OCHr-C O-QR where R is an organic radical selected from the group consisting of the substituted and unsubstituted alkyl, cycloalkyl, aryl, heterocyclic and polyalkoxy groups, and a textile lubricant.

5. The process of conditioning yarn composed of or containing cellulose acetate to render it more amenable to textile operations including knitting, weaving, spinning, and the like, which comprises applying thereto a lubricating and softening composition containing as its essential lubricating and softening component fl-methoxy ethyl tetrahydrofurfuryloxy acetate.

6. The process of conditioning yarn composed of or containing cellulose acetate to render it more amenable to textile operations including knitting, weaving, spinning, and the like, which comprises applying thereto a lubricating and softening composition containing as its essential lubricating and softening component benzyl tetrahydrofurfuryloxy acetate.

7. The process of conditioning yarn composed of or containing cellulose acetate to render it more amenable to textile operations including knitting, weaving, spinning, and the like, which comprises applying thereto a lubricating and softening composition containing as its essential lubricating and softening component p-butoxy ethyl tetrahydrofurfuryloxy acetate.

8. Textile yarns amenable to textile operations including knitting, weaving, spinning, and the like, impregnated with a lubricant containing as its essential lubricating and softening component an ester of iurfuryloxy and tetrahydroiuriuryloxy acetic acids having the general formulas:

H:CC Hg where R is an organic radical selected irom the group consisting of the substituted and unsube stituted alkyl, cycloalkyl, aryl, heterocyclic and polyalkoxy groups.

9. Textile yarns composed of or containing organic derivatives of cellulose amenable to textile operations including knitting, weaving, spin ning, and the like impregnated with a condition ing agent comprising an ester of furiuryloxy and tetrahydrofurfuryloxy acetic acids havingthe general formulas:

H,coH,

H-- n-cm-ocm-co-oa HCCH I n -om-oone-oo-o R 12 v where R is an organic radical selected fromthe group consisting of the substituted and unsubstituted alkyl, cycloalkyl, aryl, heterocyclic and polyalkoxy groups.

10. Textile yarns composed of or containing organic derivatives of cellulose amenable to textile operations including knitting, weaving, spinning, and the like impregnated with a conditioning agent comprising an ester of furfuryloxy and tetrahydrofuriuryi-om acetic acids having the general formulas:

, where is an organic radical selected from the group consisting of the substituted and unsubstituted alkyl, cycloalkyl, aryl, heterocyclic and polyalkoxy groups, and a textile lubricant.

11. Textile yarns composed of or containing cellulose acetate amenable to textile operations including knitting, weaving, spinning, and the like. impregnated with a lubricant comprising p-methoxy ethyl tetrahydrofurfuryloxyacetate.

12. Textile yarns composed of or containing 7 cellulose acetate amenable to textile operations 

